Self-sensing array of microcantilevers chemical detection

ABSTRACT

The invention provides a chemical detection system for detecting at least one target chemical species, including a self-sensed cantilevered probe array having a plurality of self-sensed cantilevered probes, at least one chemical-sensitive coating material applied to at least one cantilevered probe in the cantilevered probe array, and an interface circuit that is coupled to the cantilevered probe array. At least one cantilevered probe in the cantilevered probe array exhibits a shifted cantilevered probe response when the cantilevered probe array is exposed to the target chemical species and the interface circuit actuates the cantilevered probe. A handheld chemical detection system and a method of operation are also disclosed.

CROSS-REFERENCE TO RELATED APPLICATIONS

This utility application claims the priority benefit of, and herebyincorporates by reference in its entirety, the applicant's prior U.S.Provisional Application No. 60/512,504, filed Oct. 17, 2004.

FIELD OF THE INVENTION

This invention relates generally to chemical-sensing methods, and inparticular, relates to a method and system for sensing specificchemicals and biological materials using an array of piezoelectricallydriven cantilevered probes with selectively disposed chemical sensitivecoatings.

BACKGROUND OF THE INVENTION

Micromachined cantilevers are used in atomic force microscopy (AFM) forsurface scanning and for chemical, biological, and other sensingapplications. Micromachined cantilevers may become the basis forspecialized, ultraminiature, ultrasensitive sensors for detection ofspecific target chemical species such as chemical compounds, bioactiveagents, or toxins. Miniaturized chemical sensors hold promise forapplications needing sensitive chemical detection, quality control ofmaterials processing, and measurements of small or limited quantities ofa chemical or biological material. Resonance-based detection has beendemonstrated specifically for sensing mercury vapor, ultravioletradiation, relative humidity, magnetic susceptibility, and sub-nanogrammasses.

AFM is a method of measuring surface topography on a scale typicallyfrom a few angstroms or less to a hundred micrometers or more. Thetechnique involves imaging a sample through the use of a probe or tipsuspended from one end of a microcantilever. A surface is probed withthe tip, and the interaction between the tip and sample is measured.Physical topography, surface chemistry, charge density, magneticproperties, local temperature and other surface properties can beanalyzed.

Lasers can be used for optical detection of cantilever movement, thoughAFM systems using lasers require comparably high power on the order ofmilliwatts, need alignment, have limited resolution, and are prone todrift because of the size of the optical path. Current systems typicallyrequire external lighting for sample illumination and setup, and are notvery compact because of the long optical path, the need to have thephotodetector at an ample distance from the sample, and constrainedviewing and positioning systems for optical alignment. Sample testing inliquids such as water or saline solution presents additionaldifficulties for optical sensing due to aberrations and refraction ofthe light beam traversing the fluid.

Lasers have been used to detect frequency changes of a microcantileverthat is oscillated by a piezoelectric transducer, as taught in “MicrobarSensor,” Wachter et al., U.S. Pat. No. 5,445,008 issued Aug. 29, 1995.Oscillation frequency changes are detected by a center-crossingphotodiode that responds to a laser diode beam reflected from themicrocantilever surface resulting in an output frequency from thephotodiode that is synchronous with the microcantilever frequency.

AFM systems using microcantilevers and laser detection have been usedfor analyzing explosive gas molecules adsorbed onto themicrocantilevers, as described in “Microcantilever Detector forExplosives,” Thundat, U.S. Pat. No. 5,918,263 issued Jun. 29, 1999.Analysis can be made of the laser beam reflected by the heat-induceddeflection and transient resonant response of the microcantilever.

Because power efficiency is important to the size, lifetime, and utilityof a cantilever sensor, alternative detection schemes to those usinglasers have been proposed. Notably, capacitive systems are beingdeveloped to monitor cantilever deflection. While a low-power option,capacitive cantilever sensing is most suitable under vacuum conditionsto avoid excessive air damping between the two electrodes of thecapacitor. Other limitations of capacitive schemes include smalltolerances for fabrication and coatings of a cantilever, a reliance on asmall sensing gap size, and difficulties with sensing in liquidsolutions.

In an alternative sensing scheme to optical detection or capacitivesensing, AFM systems in a vibrating or tapping mode may use actuatedpiezoresistive cantilevers. Piezoresistive sense methods are morecompact than optical systems, though they can self-heat and cause drift.Furthermore, piezoresistive sensing typically consumes large portions ofavailable power when used in a portable device. A typical piezoresistivecantilever, which also can use milliwatts of power, is amicro-electrical-mechanical-system (MEMS) device, micromachined frombulk silicon with a piezoelectric film patterned along a portion of themicrocantilever. At the free end of the cantilever is a tip withnanometer-scale radius, optimally shaped to probe the sample surface.The microcantilever is displaced by voltage applied to the piezoelectricactuator, resulting in a controlled vertical movement of the tip.Control electronics drive the microcantilever while simultaneouslypositioning it vertically to track the sample topography and follow thesurface features. A macro-scale position actuator may be used to nullthe position of the cantilever, following the topology of the sample asthe probe is scanned over the surface.

Chemicals can be sensed based on frequency shifts of microcantileverstreated with a compound-selective substance, as disclosed in“Microcantilever Sensor,” Thundat et al., U.S. Pat. No. 5,719,324 issuedFeb. 17, 1998. A microsensor with a cantilever attached to apiezoelectric transducer is capable of detecting changes in theresonance frequency and the bending of the vibrated cantilever in amonitored atmosphere. Upon insertion into a monitored atmosphere,molecules of a targeted chemical to be sensed attach to the treatedregions of the microcantilever resulting in a change in oscillating massas well as a change in microcantilever spring constant therebyinfluencing the resonant frequency of the microcantilever oscillation.

Oscillating silicon nitride cantilevered beams coated with a thin goldfilm have been used to detect mercury vapor in air due to changes incantilever resonant frequency and stress levels induced in the goldoverlayer as described by Thundat, et al., in “Detection of MercuryVapor Using Resonating Microcantilevers,” Appl. Phys. Lett. 66 (13), 27Mar. 1995, pp. 1695-1697. An uncoated microcantilever can be used forchemical sensing by exciting charge carriers into or out of surfacestates with discrete photon wavelengths as disclosed by Thundat, et al.,in “Uncoated Microcantilevers as Chemical Sensors,” U.S. Pat. No.6,212,939, issued Apr. 10, 2001. Attempts at DNA sequencing anddetection using an AFM is described by Allen in “Method and Apparatusfor DNA Sequencing Using a Local Sensitive Force Detector,” U.S. Pat.No. 6,280,939, issued Aug. 28, 2001.

An exemplary cantilever with a piezoelectric drive and a piezoresistivesense is disclosed in “Atomic Force Microscope for High Speed ImagingIncluding Integral Actuator and Sensor,” Minne et al., U.S. Pat. No.5,883,705 issued Mar. 16, 1999, and “Cantilever for Scanning ProbeMicroscope Including Piezoelectric Element and Method of Using theSame,” Minne et al., U.S. Pat. No. 5,742,377 issued Apr. 21, 1998. Whenthe scanning probe microscope (SPM) operates in the constant force mode,the piezoelectric element is used to control the tip-sample separation.Since the resonant frequency of the piezoelectric element issubstantially higher than that of conventional piezoelectric tubescanners, much higher scan rates can be achieved. When the SPM operatesin the dynamic or intermittent contact mode, a superimposed AC-DC signalis applied to'the piezoelectric element, and the latter is used tovibrate the cantilever as well as to control the tip-sample spacing.

Piezoelectrically driven cantilevers have been proposed to eliminate theneed for external actuators. An exemplary self-actuating cantilever isdescribed in “Active Probe for an Atomic Force Microscope and Method ofUse Thereof,” Adderton et al., U.S. Pat. No. 6,530,266 issued Mar. 11,2003 and “Atomic Force Microscope for High Speed Imaging IncludingIntegral Actuator and Sensor,” Adderton et al., U.S. Pat. No. 6,189,374issued Feb. 20, 2001. This system includes a self-actuated cantileverhaving a Z-positioning element integrated therewith and an oscillatorthat oscillates the self-actuated cantilever at a frequency generallyequal to a resonant frequency of the self-actuated cantilever.

In response to the growing interest in using cantilevers for chemicalsensing, researchers are developing systems with multiple cantileversensors or modular sensor array systems to characterize larger numbersof material samples more quickly. An example of an system of multiplecantilevers in a substantially linear configuration that usesindividually-selectable cantilevers with a different resonance frequencyfor each is disclosed in “Multiprobe and Scanning Probe Microscope,”Shimizu et al., U.S. Pat. No. 6,469,293 issued Oct. 22, 2002. A modularsensor array system has been suggested for rapid deposition of samplechemicals on sensor arrays in “Sensor Array-Based System and Method forRapid Materials Characterization,” Mansky et al., U.S. Pat. No.6,535,824, issued Mar. 18, 2003 and “Sensor Array for Rapid MaterialsCharacterization,” Mansky et al., U.S. Pat. No. 6,535,822, issued Mar.18, 2003. One intended goal is to eliminate the need for multiplematerials characterization machines and the need forapplication-specific active circuitry within the sensor arraysthemselves.

In light of the discussion above, an improved system for sensingchemicals is desirable that is more compact and power-efficient thanpiezoresistively or optically sensed AFM cantilevers, does not requireoff-chip actuation for frequency measurements, does not requireindividual addressing of each cantilever to determine the naturalfrequencies, is capable of operating in liquid or gas, and generatesless unwanted heat than other AFM cantilever systems. Cantilevers needto be small and light for rapid detection of minute concentrations oftarget chemicals and biomaterials. Therefore, a desirable method andsystem for chemical sensing incorporates these improvements andovercomes the deficiencies described above.

SUMMARY OF THE INVENTION

One aspect of the invention provides a chemical detection system fordetecting at least one target chemical species. The system includes aself-sensed cantilevered probe array with a plurality of self-sensedcantilevered probes; one or more chemical-sensitive coating materialsapplied to at least one cantilevered probe in the cantilevered probearray; and an interface circuit coupled to the cantilevered probe array.One or more chemical-sensitive coated cantilevered probes in thecantilevered probe array exhibit a shifted cantilevered probe responsewhen the cantilevered probe array is exposed to the target chemicalspecies and is actuated by the interface circuit.

Another aspect of the invention is a method of chemical detection. Aself-sensed cantilevered probe is exposed to a target chemical speciesand the exposed cantilevered probe array is actuated. A cantileveredprobe response from at least one self-sensed cantilevered probe in thecantilevered probe array is detected, and the target chemical species isdetermined based on the detected cantilevered probe response.

Another aspect of the invention is a handheld system for sensing atarget chemical species including an enclosure, a self-sensedcantilevered probe array coupled to the enclosure, at least onechemical-sensitive coating material applied to at least one cantileveredprobe in the cantilevered probe array, and an interface circuit coupledto the cantilevered array. The enclosure includes an inlet port for theingression of the target chemical species and an outlet port for theegression of the target chemical species. The cantilevered probe arrayincludes a plurality of self-sensed cantilevered probes. At least onecantilevered probe in the cantilevered probe array exhibits a shiftedcantilevered probe response when the cantilevered probe array is exposedto the target chemical species and is actuated by the interface circuit.

BRIEF DESCRIPTION OF THE DRAWINGS

The current invention is illustrated by the accompanying drawings ofvarious embodiments and the detailed description given below. Thedrawings should not be taken to limit the invention to the specificembodiments, but are for explanation and understanding. The detaileddescription and drawings are merely illustrative of the invention ratherthan limiting, the scope of the invention being defined by the appendedclaims and equivalents thereof. The foregoing aspects and otherattendant advantages of the present invention will become more readilyappreciated by the detailed description taken in conjunction with theaccompanying drawings. Various embodiments of the present invention areillustrated by the accompanying figures, wherein:

FIG. 1 illustrates a chemical detection system for detecting at leastone target chemical species, in accordance with one embodiment of thecurrent invention;

FIG. 2 illustrates a self-sensed cantilevered probe array, in accordancewith one embodiment of the current invention;

FIG. 3 is a schematic diagram of a cantilevered probe array withseries-connected cantilevered probes electrically connected to a pair ofcantilevered probe array drive pads, in accordance with one embodimentof the current invention;

FIG. 4 is a schematic diagram of a cantilevered probe array withparallel-connected cantilevered probes electrically connected to a pairof cantilevered probe array drive pads, in accordance with oneembodiment of the current invention;

FIG. 5 is a schematic diagram of a cantilevered probe array with anetwork of series-connected and parallel-connected cantilevered probeselectrically connected to a pair of cantilevered probe array drive pads,in accordance with one embodiment of the current invention;

FIG. 6 a is a schematic diagram of a controller and an interface circuitconnected to a self-sensed cantilevered probe array, in accordance withone embodiment of the current invention;

FIG. 6 b is a plot of cantilevered probe responses from a self-sensedcantilevered probe array scanned through a predetermined frequencyrange, in accordance with one embodiment of the current invention;

FIG. 7 illustrates a method for applying a chemical-sensitive coatingmaterial to a cantilevered probe array with a mask, in accordance withone embodiment of the current invention;

FIG. 8 illustrates a top view of a self-sensed cantilevered probeincluding a selectively deposited coating, a heater, and a speciesattraction electrode;

FIG. 9 illustrates a handheld system for sensing a target chemicalspecies, in accordance with one embodiment of the current invention;

FIG. 10 is a flow chart of a method for chemical detection, inaccordance with one embodiment of the current invention; and

FIG. 11 is a flow chart of a method for chemical detection, inaccordance with another embodiment of the current invention.

DETAILED DESCRIPTION OF THE INVENTION

FIG. 1 illustrates a chemical detection system for detecting at leastone target chemical species, in accordance with one embodiment of thepresent invention. The chemical detection system 10 includes aself-sensed cantilevered probe array 20 with a plurality of self-sensedcantilevered probes 30. Self-sensed cantilevered probes have suspendedcantilevered elements with a piezoelectric drive 32 comprised of adeposited layer of zinc oxide (ZnO), lead zircanate titinate (PZT), orother piezoelectric material that bends, deflects and vibrates thecantilevered element when excited or actuated with an applied drivevoltage. The piezoelectric material generates a voltage as thecantilevered probes bend or vibrate, and can be used to sensecantilevered probe motions as well as drive cantilevered probes 30,referred to herein as self-sensing. At least one chemical-sensitivecoating material 34 is applied to one or more cantilevered probes 30 incantilevered probe array 20 to allow for chemical detection andspecificity. One or more cantilevered probes 30 in cantilevered probearray 20 is coated or otherwise treated to detect target chemicalspecies 12. An interface circuit 40, which is coupled to cantileveredprobe array 20, actuates and senses motions of cantilevered probes 30.When cantilevered probe array 20 is exposed to a target chemical species12 and is actuated by interface circuit 40, one or more cantileveredprobes 30 in cantilevered probe array 20 exhibit a shifted cantileveredprobe response.

Cantilevered probes 30 in cantilevered probe array 20 arefrequency-differentiated such that cantilevered probes 30 havingdifferent masses or effective spring constants exhibit differentresonant frequencies. Cantilevered probes 30 can be manufactured, forexample, with small differences in cantilever lengths, resulting inseparations in resonant frequencies so that the resonant frequency ofeach cantilevered probe 30 in an array is able to be detected with asfew as two wires connected to cantilevered probe array 20. Thus,cantilevered probe arrays 20 with two or more cantilevered probes 30 canbe packaged and connected to interface circuit 40 with a minimal numberof bond pads, interconnection traces and bond wires to externalinterface and control electronics. Parallel arrays of cantileveredprobes 30 can be configured with elements that number from a few tomassively parallel arrays with a million or more cantilevered probes 30on one substrate or die. Groups of cantilevered probe arrays 20 may beconnected during on-chip trace definition, while wire-bonding to aleadframe or package, or at the socket or board level.

Non-overlapping, independent and orthogonal chemical-sensing effects onindividual cantilevered probes 30 in cantilevered probe array 20 may bedesirable but not necessary when many cantilevered probes 30 withvarious coatings and coating thicknesses are used for detection. Signalprocessing and pattern recognition of the resonance-frequency data frommultiple cantilever probes 30 may be employed to differentiate betweenvarious target chemical species in varying concentrations havingsometimes small and sometimes null effects. Differentiation betweensimilar chemical substances can be made and their constituency andconcentration can be determined in a system where a variety of coatingsare applied to multiple cantilevered probes 30. Chemical detectionsystem 10 can detect one or more target chemical species 12 such asmercury, hydrogen, an alcohol, water vapor, an explosive material, achemical element, a chemical compound, an organic material, an inorganicmaterial, a gaseous substance, a liquid, a biological material, a DNAstrand, a bioactive agent, a toxin, and a combination thereof. Chemicalspecies refers to any chemical or biological material.

One or more cantilevered probes 30 respond when exposed to targetchemical species 12. Cantilevered probes 30 may respond by absorbing,adsorbing, or otherwise reacting to target chemical species 12. Whenexposed to target chemical species 12, cantilevered probes 30 mayincrease or decrease in mass, or become more rigid or less rigid. In oneexample, cantilevered probe 30 comprises a patterned layer of gold. Whenexposed to mercury, the two react to form an amalgam. The gold-mercuryamalgam adds mass to cantilevered probe 30 and therefore tends todecrease the resonant frequency of cantilevered probe 30. Amalgamformation, however, increases the mechanical stiffness of cantileveredprobe 30 thereby increasing its natural resonant frequency. The twoeffects tend to cancel each other, though one effect can be madedominant by careful selection and placement of chemical-sensitivecoating material 34 on cantilevered probe 30.

Target chemical species 12, which may be located in a liquid or gascarrier 14 such as air or water, in a low-pressure gas, or a plasma, aretransported in a forced or free manner towards cantilevered probes 30where they contact surfaces of cantilevered probes 30 and invoke shiftsin resonant frequency, Q factor, impedance, or deflection amplitudes.

Cantilevered probe array 20 is actuated with an excitation voltageapplied to piezoelectric drive 32 disposed on each cantilevered probe 30in cantilevered probe array 20. To reduce the number of externalconnections, a group of cantilevered probes 30 may be connected inseries and electrically connected to a pair of cantilevered probe arraydrive pads 24, which in turn is electrically connected to interfacecircuit 40. While this configuration can increase the series resistanceof the string, differentiation of individual cantilevered probes 30 maybe made with detection of signals at or near the resonant frequency ofselected cantilevered probe 30. Alternatively, a group of cantileveredprobes 30 may be connected in parallel and electrically connected to apair of cantilevered probe array drive pads 24, increasing the effectivecapacitance and decreasing the effective resistance, while stillallowing differentiation of individual cantilevered probe responsesbased on frequency. Alternatively, cantilevered probes 30 may beconnected in a network of series-connected and parallel-connectedcantilevered probes with frequency-identifiable addressable elements.

Interface circuit 40 provides excitation voltages for the piezoelectricmaterial on cantilevered probes 30 and senses deflections and vibrationsof cantilevered probes 30 with the same piezoelectric material. In oneexample, interface circuit 40 includes an adjustable frequency generatorthat is scanned through a predetermined frequency range to excite one ormore cantilevered probes 30 in cantilevered probe array 20. In anotherexample, interface circuit 40 includes an impedance analyzer that isscanned through a resonant frequency of at least one cantilevered probe30, measuring the magnitude and phase from cantilevered probes 30 andmonitoring for any variations in the impedance as cantilevered probes 30are exposed to one or more target chemical species 12. In anotherexample, interface circuit 40 includes an oscillator circuit operatingat a resonant frequency of at least one cantilevered probe 30 incantilevered probe array 20. In another example, interface circuit 40includes an oscillator circuit operating at a predetermined frequencythat is near, yet off-resonance with respect to one or more cantileveredprobes 30 in cantilevered probe array 20, so that as the resonantfrequency of the selected cantilevered probe 30 shifts, a large outputsignal can be obtained as the resonant frequency shifts and movestowards the predetermined frequency, resulting in higher amplitudes ofvibration and therefore higher output signals. The predeterminedfrequency may be set, for example, slightly above or slightly below theresonant frequency of one of cantilevered probes 30. In another example,the amplitude of bending and vibration is monitored as cantileveredprobe 30 strikes against a fixed or adjustable mechanical stop such as apiezoelectric slab or a piezotube. In another example, interface circuit40 includes an impulse circuit for applying an electrical impulse tocantilevered probe array 20, and ring-down of cantilever probes 30 ismonitored. In another example, noise such as pink noise or white noiseis applied to excite cantilevered probe array 20. In another example,interface circuit 40 includes a network analyzer for detecting signalsfrom cantilevered probe array 20. Interface circuit 40 or controller 50may include a fast Fourier transform generator to perform a fast Fouriertransform (FFT) on the shifted cantilevered probe response and providerespective frequencies of cantilevered probes 30 in cantilevered probearray 20 for correlation with previously measured probe responses anddetermination of target chemical species 12.

Interface circuit 40 detects shifted cantilevered probe responses fromone or more actuated cantilevered probes 30 in cantilevered probe array20. Shifted cantilevered probe responses include, for example, a shiftin a resonant frequency of one or more cantilevered probes 30, a shiftin a quality (Q) factor of one or more cantilevered probes 30, a shiftin impedance of one or more cantilevered probes 30, a shift indeflection amplitude of one or more cantilevered probes 30, or acombination thereof. With exposure to target chemical species 12, one ormore cantilevered probes 30 in cantilevered probe array 20 can exhibitshifts. Similarly, with exposure to more than one target chemicalspecies 12, one or more cantilevered probes 30 in cantilevered probearray 20 may exhibit shifts from which multiple target chemical species12 can be determined.

A controller 50 such as a central processing unit (CPU), a digitalsignal processor (DSP), a microcontroller, or a field-programmable gatearray (FPGA) may be included in chemical detection system 10 to executeprogrammed code and provide monitoring, controlling and analyzingfunctions. Controller 50 is in electrical communication with interfacecircuit 40 and may be located, for example, on substrate 22 along withcantilevered probe array 20, within enclosure 60 on the same circuitboard or in the same package as cantilevered probe array 20, or locatedremotely with respect to enclosure 60. Controller 50 may internallycontain the functions and capabilities of interface circuit 40.Controller 50 receives shifted cantilevered probe responses from a setof one or more cantilevered probes 30 in cantilevered probe array 20.Target chemical species 12 may be determined based on the shiftedcantilevered probe response using, for example, an algebraic model thatrelates shifts in cantilevered probe responses to target chemicalspecies and concentration. Alternatively, target chemical species 12 maybe determined based on a comparison between the shifted cantileveredprobe responses and a reference set of cantilevered probe responses.Such reference sets can be obtained by exposing cantilevered probes 30to controlled environments with known target chemical species andconcentrations during calibration at the factory or on site. Controller50 can determine one or more target chemical species 12 through patternrecognition techniques, statistical processes, and fuzzy logic withcomparison to the reference set of cantilevered probe responses. Thereference set of cantilevered probe response comprises, for example, alearned set obtained from shifts in cantilevered probe responses bycantilevered probes 30 that are exposed to known target chemical speciesand concentrations under controlled laboratory or factory environments.

Chemical-sensitive coating material 34 is applied to at least a portionof one or more cantilevered probes 30 of cantilevered probe array 20.For example, chemical-sensitive coating material 34 may be applied tothe topside or bottom side of one or more cantilevered probes 30 or toportions thereof. Chemical-sensitive coating material 34 includes, forexample, an epoxy resin such as Novolac™, a fluoropolymer such asFluoroPel™, a gold layer, a palladium layer, an alcohol-absorbentpolymer, a water-absorbent material, a chemical-sensitive polymer, achemical-sensitive layer, a biosensitive material, a thiol, andcombinations thereof.

Various application methods are used to deposit or apply coatingmaterials and to treat surfaces of cantilevered probes 30.Chemical-sensitive coating materials 34 comprise, for example, a dippedcoating, a sprayed coating, or a dispensed coating disposed on at leastof portion of one or more cantilevered probes 30. An exemplarychemical-sensitive coating material 34 includes a masked coatingdisposed on a portion of one or more cantilevered probes 30. In analternative application method, a non-homogeneous coating material isapplied to a set of cantilevered probes 30 in cantilevered probe array20, such that constituents of the non-homogeneous coating material aredeposited on cantilevered probes 30 with suitable variations incomposition, coverage, and thickness.

In one embodiment of the present invention, chemical detection system 10includes one or more reference cantilevered probes in the cantileveredprobe array. The reference cantilevered probe provides a referencecantilevered probe response when cantilevered probe array 20 is exposedto target chemical species 12. Reference cantilevered probes are formed,for example, with no coating materials disposed thereon to reduce oreliminate sensitivity to target chemical species 12. Alternatively,reference cantilevered probes have an inert coating disposed on thesurface to reduce or eliminate sensitivity to target chemical species12. Alternatively, one or more reference cantilevered probes aremechanically isolated from exposure to target chemical species 12 whileother portions of cantilevered probe array 20 are exposed.

In cases where heating of select cantilevered probes 30 burns off,evaporates off, or otherwise cleans and resets cantilevered probe 30 toa nascent condition, a resistive heater 36 may be coupled to at leastone cantilevered probe 30 in the cantilevered probe array 20. Resistiveheater 36 may be formed with a resistive layer disposed on the surfaceof or formed within cantilevered probe 30. Exemplary resistive heaters36, which may be connected in series or parallel or individuallyconnected are formed on one, several, or all cantilevered probes 30within cantilevered probe array 20. Resistive heaters 36 also may beused to react a target chemical species on cantilevered probe 30 byheating the probe to a predetermined temperature where the reaction canoccur. Alternatively, resistive heaters 36 may be used to ignite ordeflagrate condensate of explosive vapors on cantilevered probes 30.

Species attraction electrodes 38 disposed on cantilevered probes 30 canbe used to apply voltage to preferentially attract target chemicalspecies 12 or to allow the monitoring of electrochemical reactions inthe vicinity of cantilevered probes 30. Species attraction electrodes38, which may be disposed on one or more cantilevered probes 30 incantilevered probe array 20, allow the application of a speciesattraction potential.

Exemplary chemical detection system 10 contains one or more cantileveredprobe arrays 20 in an enclosure 60, which includes an inlet port 62 andan outlet port 64 for transport of target chemical species 12 andcarriers 14. Target chemical species 12 enters enclosure 60 throughinlet port 62 and is exposed to cantilevered probe array 20. Targetchemical species 12 or by-products thereof exit through outlet port 64.Enclosure 60 may include filters, scrubbers, and other media treatmentelements to aid in the detection of target chemical species 12.

A transport mechanism 66 such as a pump or a fan with ductwork or pipingmay be included for transporting target chemical species 12 tocantilevered probe array 20.

A concentrator 68 such as a pressurizing system or a condenser andheater system may be included to concentrate target chemical species 12proximal to cantilevered probe array 20 for detection of target chemicalspecies 12.

Chemical detection system 10 may be connected to a local area network(LAN), a wide area network (WAN), the Internet, or other networkedcommunication system via one or more wired or wireless connections.

Chemical detection system 10 may be installed, for example, into an airhandling system of a building or airport that has many inlets, into astandalone unit with a portal for chemical detection, and into handheldunits for portable use. Chemical detection system 10 may be installed inshipping containers and crates during storage and transit for chemicaldetection and monitoring.

FIG. 2 illustrates a self-sensed cantilevered probe array, in accordancewith one embodiment of the present invention. Self-sensed cantileveredprobe array 20 includes a plurality of cantilevered probes 30 on asubstrate 22. At least one chemical-sensitive coating material 34 isapplied to one or more cantilevered probes 30 in cantilevered probearray 20. Variations in length or thickness of cantilevered probes 30and variations in the thickness and coverage of applied coatings allowfrequency differentiation between cantilevered probes withincantilevered probe array 20.

Cantilevered probes 30 may have a rectangular shape, though other shapesmay be suitably used such as a pointed cantilever, a V-shapedcantilever, a triangular-shaped cantilever, a dual-arm cantilever, or abalanced cantilever. Cantilevered probes 30 may be arranged and attachedto substrate 22 in an array of cantilevered beams, the cantilevers beingall identical, all different, or some combination thereof.

Cantilevered probe array 20 is actuated with an excitation voltageapplied to a piezoelectric drive 32 of piezoelectric material disposedon each cantilevered probe 30. Cantilevered probes 30 may beseries-connected to a pair of cantilevered probe array drive pads 24 onsubstrate 22. Alternatively, cantilevered probes 30 may beparallel-connected to the pair of cantilevered probe array drive pads24. Alternatively, cantilevered probe array 20 may comprise a network ofseries-connected and parallel-connected cantilevered probes electricallyconnected to the pair of cantilevered probe array drive pads 24. Morethan one group or array of cantilevered probes 30 may be included onsubstrate 22. Substrate 22 may have through-wafer vias for backsideconnection.

Substrate 22 includes a semiconductor substrate such as a silicon wafer,a silicon-on-insulator (SOI) wafer, a glass substrate, or other suitablesubstrate for forming cantilevered probes 30 thereon. Cantileveredprobes 30 comprise materials such as silicon, polysilicon, siliconnitride, a metal film, a metal sheet, a zinc oxide film, a PZT film, apolymeric layer, and combinations thereof. For example, a zinc oxidefilm is deposited on a layer of single-crystal silicon, patterned, andetched. Conductive layers for top and bottom electrodes,interconnections, and heater connections are deposited and etchedaccordingly. Definition of cantilevered probes 30 with a photomask andassociated lithographic sequences along with deep reactive ion etching(D-RIE) or anisotropic etching of the cantilevers and substrate allowsthe formation and freeing of silicon cantilevers with interconnected ZnOelectrodes in series, parallel, and series-parallel configurations.Excitation and detection of the cantilevers occur with voltages appliedto the piezoelectric material and detection thereof.

Chemical-sensitive coating material 34 is applied to at least a portionof one or more cantilevered probes 30. The chemical-sensitive coatingmaterial includes, for example, an epoxy resin, a fluoropolymer, a goldlayer, a palladium layer, an alcohol-absorbent polymer, awater-absorbent material, a chemical-sensitive polymer, achemical-sensitive layer, a biosensitive material, a thiol, and acombination thereof. Chemical-sensitive coating material 34 may beapplied, for example, with techniques such as dipping, spraying, ordispensing the coating on at least a portion of one or more cantileveredprobes. The chemical-sensitive coating material may be applied onto aportion of one or more cantilevered probes with the use of stencil masksor photomasks and photolithographic patterning techniques.Chemical-sensitive coating material 34 may be applied, for example,using standard sputtering and other deposition techniques known in theart.

Multiple masking sequences can be used to apply multiple coatingmaterials. Alternatively, multiple-component chemical-sensitive coatingmaterials 34 may comprise a non-homogeneous coating material applied toa set of cantilevered probes 30 in the cantilevered probe array 20,applied in such a way that variations in coating thickness andcomposition occur when they are deposited.

When exposed to target chemical species 12, one or more cantileveredprobes 30 in cantilevered probe array 20 may undergo an electrical or amechanical shift, such as a shifted resonant frequency, a shifted Qfactor, a shifted impedance, or a shifted deflection amplitude.

Cantilevered probe array 20 may include one or more referencecantilevered probes 30 r to provide a reference cantilevered proberesponse when cantilevered probe array 20 is exposed to target chemicalspecies 12. For example, reference cantilevered probes may be uncoated,coated with an inert material, or otherwise protected from exposure totarget chemical species 12.

FIG. 3 is a schematic diagram of a cantilevered probe array withseries-connected cantilevered probes electrically connected to a pair ofcantilevered probe array drive pads, in accordance with one embodimentof the present invention. Two or more cantilevered probes 30 in acantilevered probe array 20 are connected in series to a pair ofcantilevered probe array drive pads 24. Electrodes above and below thepiezoelectric material on each cantilevered probe 30 are connected inseries with electrodes above and below the piezoelectric material onother cantilevered probes 30 in the set. In the example illustrated,cantilevered probes 30 a, 30 b, . . . 30 n represent a plurality ofseries-connected cantilevered probes with piezoelectric drives 32 a, 32b, . . . 32 n that are frequency-differentiated with fundamentalresonant frequencies f1, f2, . . . fn, respectively. Each cantileveredprobe 30 a, 30 b, . . . 30 n may have one or more chemical-sensitivecoating materials 34 a, 34 b, . . . 34 n coated thereon. When activated,for example, with an interface circuit (not shown) that scans throughthe resonant frequencies of one or more cantilevered probes, eachcantilevered probe within the scanned frequency range is, in turn,excited and oscillated by the interface circuit as the frequency of theoscillator or frequency generator is scanned through its resonantfrequency. Multiple groups of series-connected cantilevered probes 30may be further connected in series or in parallel to cantilevered probearray drive pads 24 or to other sets of drive pads.

FIG. 4 is a schematic diagram of a cantilevered probe array withparallel-connected cantilevered probes electrically connected to a pairof cantilevered probe array drive pads, in accordance with oneembodiment of the present invention. Two or more cantilevered probes 30are connected in parallel to a pair of cantilevered probe array drivepads 24. Electrodes above and below the piezoelectric material on eachcantilevered probe 30 are connected in parallel with electrodes aboveand below the piezoelectric material on other cantilevered probes 30 inthe set. In the example illustrated, cantilevered probes 30 a, 30 b, . .. 30 n represent a plurality of parallel-connected cantilevered probeswith piezoelectric drives 32 a, 32 b, . . . 32 n that arefrequency-differentiated with fundamental resonant frequencies f1, f2, .. . fn, respectively. Each cantilevered probe 30 a, 30 b, . . . 30 n mayhave one or more chemical-sensitive coating materials 34 a, 34 b, . . .34 n coated thereon. When activated, for example, with an interfacecircuit (not shown) that scans through the resonant frequencies of oneor more cantilevered probes, each cantilevered probe is, in turn,excited and oscillated by the interface circuit as the frequency of theoscillator or frequency generator is scanned through the resonantfrequency. Multiple groups of parallel-connected cantilevered probes 30may be further connected in series or in parallel to cantilevered probearray drive pads 24 or to other sets of drive pads.

FIG. 5 is a schematic diagram of a cantilevered probe array with anetwork of series-connected and parallel-connected cantilevered probeselectrically connected to a pair of cantilevered probe array drive pads,in accordance with one embodiment of the present invention. A pluralityof cantilevered probes 30 is connected in a network of series and/orparallel sets of cantilevered probes 30 to a pair of cantilevered probearray drive pads 24. In the example illustrated, cantilevered probes 30a, 30 b, . . . 30 n represent series-connected and parallel-connectedcantilevered probes with piezoelectric drives 32 a, 32 b, . . . 32 nthat are frequency-differentiated with fundamental resonant frequenciesf1, f2, . . . fn. Each cantilevered probe 30 a, 30 b, . . . 30 n mayhave one or more chemical-sensitive coating materials 34 a, 34 b, . . .34 n coated thereon. When activated, for example, with an interfacecircuit (not shown) that scans through the resonant frequencies of oneor more cantilevered probes 30, each cantilevered probe 30 is, in turn,excited and oscillated by the interface circuit as the frequency of theoscillator or frequency generator is scanned through the resonantfrequency. Multiple groups of networked cantilevered probe arrays 20 maybe located on the same substrate and connected to other pairs of drivepads.

FIG. 6 a is a schematic diagram of a controller and an interface circuitconnected to a self-sensed cantilevered probe array, in accordance withone embodiment of the present invention. Controller 50 is connected tointerface circuit 40 that drives and senses a plurality of self-sensedcantilevered probes 30 in a cantilevered probe array 20. It should beobserved that cantilevered probe array 20 may be electrically connectedto interface circuit 40 with as few as two cantilevered probe arraydrive pads 24. At least one cantilevered probe 30 in cantilevered probearray 20 exhibits a shifted cantilevered probe response whencantilevered probe array 20 is exposed to target chemical species 12 andcantilevered probe array 20 is actuated by interface circuit 40.

Interface circuit 40 actuates cantilevered probe array 20 with anexcitation voltage applied to a piezoelectric material disposed on eachcantilevered probe 30 in the cantilevered probe array 20. In oneexample, interface circuit 40 includes an adjustable frequency generatorthat is scanned through a predetermined frequency range. In anotherexample, interface circuit 40 includes an impedance analyzer that isscanned through a resonant frequency of one or more cantilevered probes30 in cantilevered probe array 20. In another example, interface circuit40 includes an oscillator circuit operating at a resonant frequency ofat least one cantilevered probe in the cantilevered probe array. Inanother example, interface circuit 40 includes an oscillator circuitoperating at a predetermined frequency that is set to be off-resonancewith respect to at least one cantilevered probe 30 in cantilevered probearray 20. In another example, interface circuit 40 includes controlcircuitry to monitor the amplitude of bending and vibration ascantilevered probe 30 strikes against a fixed or adjustable mechanicalstop. In another example, interface circuit 40 comprises an impulsecircuit for applying an electrical impulse to all cantilevered probes 30in cantilevered probe array 20. In another example, interface circuit 40or controller 50 includes a fast Fourier transform generator to performa fast Fourier transform on the shifted cantilevered probe response.Interface circuit 40 detects a shifted cantilevered probe response fromone or more actuated cantilevered probes 30 such as a shifted resonantfrequency, a shifted Q factor, a shifted impedance, or a shifteddeflection amplitude.

Controller 50 receives a shifted cantilevered probe response from a setof one or more cantilevered probes 30 in cantilevered probe array 20.The target chemical species is determined based on the shiftedcantilevered probe response. For example, the target chemical speciesmay be determined based on a comparison between the shifted cantileveredprobe response and a reference set of cantilevered probe responses. Thereference set of cantilevered probe responses comprises, for example, alearned set obtained during the calibration of the chemical-sensingsystem or from a statistical database of cantilevered probe responses.

To cancel out common mode effects such as temperature, one of thecantilevered probes 30 in the cantilevered probe array 20 may be areference cantilevered probe 30 r, wherein the reference cantileveredprobe 30 r provides a reference cantilevered probe response whencantilevered probe array is exposed to target chemical species 12.

FIG. 6 b shows an illustrative plot of cantilevered probe responses froma self-sensed cantilevered probe array scanned through a predeterminedfrequency range, in accordance with one embodiment of the presentinvention. When activated, for example, with an interface circuit thatscans through the resonant frequencies of one or more cantileveredprobes, each cantilevered probe is, in turn, excited and oscillated bythe interface circuit as the frequency of the oscillator or frequencygenerator is scanned through the resonant frequency. Depending on thetype and amount of a target chemical species and the coating on thecantilevered probe, the cantilevered probes in the array may exhibitshifted cantilevered probe responses such as a shifted resonantfrequency, a shifted Q factor, a shifted impedance, a shifted deflectionamplitude, or a combination thereof.

Output curve 90 shows exemplary output signals from an array ofcantilevered probes excited through a frequency range that includes aresonant frequency of each of the cantilevered probes in the array.Output curve 90 shows a baseline or reference set of resonant peaks 90a, 90 b, 90 c, 90 d, 90 e, 90 f, 90 g and 90 n corresponding to a set ofeight frequency-differentiated cantilevered probes with nominally equalfrequency separations between the cantilevered probes. When thecantilevered probe array is exposed to a target chemical species and isactuated by the interface circuit, at least one cantilevered probe inthe cantilevered probe array exhibits a shifted cantilevered proberesponse.

Exemplary output curve 92 shows resonant peaks 92 a, 92 b, 92 c, 92 d,92 e, 92 f, 92 g and 92 n corresponding to the set of eightfrequency-differentiated cantilevered probes after exposure to one ormore target chemical species. In the example illustrated, resonant peak92 a of the first cantilevered probe is shifted downwards from resonantpeak 90 a after chemical exposure. Resonant peak 92 b of the secondcantilevered probe is shifted higher than resonant peak 90 b. Resonantpeak 92 c of the third cantilevered probe remains the same as resonantpeak 90 c. Resonant peak 92 d of the fourth cantilevered probe has alower Q factor than resonant peak 90 d after chemical exposure. Resonantpeak 92 e of the fifth cantilevered probe has a higher Q factor thanresonant peak 90 e after chemical exposure. Resonant peak 92 f has anamplitude less than that of resonant peak 90 f after chemical exposure,and resonant peak 92 g has an amplitude greater than that of resonantpeak 90 g after chemical exposure. Resonant peak 92 n exhibits acombination of shifts in frequency, Q factor and amplitude afterchemical exposure.

An additional resonant peak 92r corresponding to a referencecantilevered probe shows no change in cantilevered probe response afterexposure to the target chemical species compared to resonant peak 90 rcorresponding to the reference cantilevered probe prior to exposure.

FIG. 7 illustrates a chemical-sensitive coating material applied to acantilevered probe array with a mask, in accordance with one embodimentof the present invention. A stencil mask 80 including at least oneaperture 82 is positioned on or above a surface of a self-sensedcantilevered probe array 20 having a plurality of self-sensedcantilevered probes 30. A chemical-sensitive coating material 34 isselectively applied to cantilevered probe array 20 through apertures 82.In the example shown, cantilevered probes 30 a, 30 b, . . . 30 n areselectively coated with chemical-sensitive coating material 34 byspraying the material through stencil mask 80 and then dryingchemical-sensitive coating material 34 a, 34 b, . . . 34 n oncantilevered probes 30 a, 30 b, . . . 30 n, respectively. A referencecantilevered probe 30 r is shown with no coating, having been maskedwith stencil mask 80 during spraying.

In this example, cantilevered probes 30 a, 30 b, . . . 30 n arenominally the same size and thickness. Frequency differentiation forthis set of cantilevered probes is achieved by varying the area of thecantilevered probes that is covered by the coating. An angled aperture82 in stencil mask 80 allows different amounts of coating material to bedisposed on each cantilevered probe, varying the mass on eachcantilevered probe and thereby changing the resonant frequenciesaccordingly. Stencil mask 80 may be used to cover cantilevered probearray drive pads 24 and other portions of substrate 22 that need not becoated. Piezoelectric drives 32 on cantilevered probes 30 a, 30 b, . . .30 n and 30 r, respectively, may be coated, partially coated, oruncoated with chemical-sensitive coating materials 34.

FIG. 8 illustrates a top view of a self-sensed cantilevered probeincluding a selectively deposited coating, a heater, and a speciesattraction electrode. A resistive heater 36′is disposed on or formed incantilevered probe 30. Resistive heater 36 allows cantilevered probe 30to be heated, for example, to initialize cantilevered probe 30 prior toexposing cantilevered probe array 20 to the target chemical species. Inanother role, resistive heater 36 may be used to burn off, deflagrate,or otherwise react a target chemical species that deposits on a surfaceof cantilevered probe 30.

In another embodiment, a species attraction electrode 38 may be disposedon cantilevered probe 30 of cantilevered probe array 20 to allow aspecies attraction potential to be applied. Species attraction electrode38 is positioned, for example, underneath or adjacent tochemical-sensitive coating material 34. Electrical connections tospecies attraction electrode 38 may be made with, for example, one endof piezoelectric drive 32, one end of resistive heater 36, or with aconnection to an independent electrical trace on substrate 22.

FIG. 9 illustrates a handheld system for sensing a target chemicalspecies, in accordance with one embodiment of the present invention.Handheld system 70 includes an enclosure 60, a self-sensed cantileveredprobe array 20, at least one chemical-sensitive coating material 34applied to at least one self-sensed cantilevered probe 30 incantilevered probe array 20, and an interface circuit 40 coupled tocantilevered probe array 20. Enclosure 60 has an inlet port 62 to allowingression of target chemical species 12 into enclosure 60 and an outletport 64 to allow egression of target chemical species 12 or a by-productthereof from enclosure 60. When cantilevered probe array 20 is exposedto target chemical species 12 and cantilevered probe array 20 isactuated by interface circuit 40, one or more cantilevered probes 30 incantilevered probe array 20 exhibit a shifted cantilevered proberesponse.

Cantilevered probe array 20 includes a plurality of cantilevered probes30 that are frequency-differentiated. The plurality of cantileveredprobes 30 in cantilevered probe array 20 is electrically connected to apair of cantilevered probe array drive pads, and one or more groups ofcantilevered probes 30 may be included within enclosure 60.

Handheld system 70 may include a controller 50 in communication withinterface circuit 40. Controller 50 receives a shifted cantileveredprobe response from a set of cantilevered probes 30 in cantileveredprobe array 20. The shifted cantilevered probe responses are analyzedand the constituency and concentration of target chemical species 12 maybe determined based on the shifted cantilevered probe response.

Cantilevered probe array 20 may include a reference cantilevered probe30 r. The reference cantilevered probe 30 r provides a referencecantilevered probe response when cantilevered probe array 20 is exposedto target chemical species 12.

One or more cantilevered probes 30 in cantilevered probe array 20 mayhave resistive heaters 36 to locally heat selected cantilevered probes30. A species attraction electrode 38 may be disposed on one or morecantilevered probes 30 in cantilevered probe array 20 to allowapplication of a species attraction potential.

Handheld system 70 may include a transport mechanism 66 such as a pump,fan or blower and ductwork or piping for transporting target chemicalspecies 12 to cantilevered probe array 20. Handheld system 70 mayinclude a concentrator 68 such as a compressor or a condenser toconcentrate target chemical species 12 proximal to one or morecantilevered probes 30 in cantilevered probe array 20.

Command and data entry input devices such as buttons, keypads, orsoftkeys, allow the selection of the function and operation of handheldsystem 70. Results of measurements are displayed on an output devicesuch as an LCD, or communicated to another analysis system through awired communication port such as a universal serial bus (USB) port orthrough a wireless communication protocol.

FIG. 10 is a flow chart of a method for chemical detection, inaccordance with one embodiment of the present invention. The chemicaldetection method includes various steps to detect and identify one ormore target chemical species with a self-sensed cantilevered probearray.

The cantilevered probes in the cantilevered probe array arefrequency-differentiated, separated in the frequency domain such thatany one of the cantilevered probes can be measured independently of theothers using, for example, a frequency generator, a frequencysynthesizer, a controlled oscillator, or an impedance analyzer when thecantilevered probes are configured in series or in parallel with othercantilevered probes. The cantilevered probe array includes, for example,at least two-series connected cantilevered probes electrically connectedto a pair of cantilevered probe array drive pads. Alternatively, thecantilevered probe array includes at least two parallel-connectedcantilevered probes electrically connected to a pair of cantileveredprobe array drive pads. Alternatively, the cantilevered probe arrayincludes a network of series-connected and parallel-connectedcantilevered probes electrically connected to a pair of cantileveredprobe array drive pads. One or more groups of cantilevered probes may beconnected to the same set of cantilevered probe array drive pads or to adifferent set of cantilevered probe array drive pads on the samesubstrate for external connection to an interface circuit.

After fabrication of the cantilevered probe array, a chemical-sensitivecoating material may be applied to one or more cantilevered probes inthe cantilevered probe array, as seen at block 100. Thechemical-sensitive coating material may include, for example, an epoxyresin, a fluoropolymer, a gold layer, a palladium layer, analcohol-absorbent polymer, a water-absorbent material, achemical-sensitive polymer, a chemical-sensitive layer, a biosensitivematerial, a thiol, and combinations thereof.

The coating material may be applied, for example, by standard depositiontechniques such as sputter depositions, electron beam depositions, orplasma-enhanced chemical vapor depositions, or by dipping, spraying ordispensing the coating material onto at least a portion of one or morecantilevered probes. The coating material may be applied, for example,with a stencil mask and selective masking of one or more cantileveredprobes and applying the chemical-sensitive coating through the mask. Asingle material may be applied through the mask.

A plurality of chemical-sensitive coating materials may be applied to aset of cantilevered probes in the cantilevered probe array. For example,multiple masks may be used for multiple coatings with different coatingmaterials on selected portions of one or more cantilevered probes.Alternatively, coating with multiple materials through a single mask maybe accomplished by spraying a non-homogenous coating material onto a setof cantilevered probes in the cantilevered probe array such thatcantilevered probes in the array are coated with substantive differencesin coating constituency, thickness, or fraction of coverage.

When a resistive heater is used, the resistive heater that is coupled toat least one cantilevered probe is heated to initialize the cantileveredprobe prior to exposing the cantilevered probe array to the targetchemical species, as seen at block 102. The resistive heater locallyheats up the cantilevered probe to an elevated temperature to evaporate,burn off, or otherwise remove residual materials from the surfaces ofthe cantilevered probe.

The array is initialized, as seen at block 104. Initialization of thearray is accomplished, for example, by running a scan through theresonant frequencies of the cantilevered probes in the cantileveredprobe array to establish a baseline or to ensure that all thecantilevered probes and the interface electronics are functioningproperly.

The target chemical species may be transported to the cantilevered probearray, as seen at block 106. Fans, blowers, or pumps may be used, forexample, to force flow of the target chemical species and a carrier gasor liquid onto the cantilevered probe array. Convective processes ornormal diffusive processes due to concentration gradients may be used,for example, to transport the target chemical species to thecantilevered probe array for detection.

The target chemical species may be concentrated proximal to thecantilevered probe array, as seen at block 108. Concentration of thetarget chemical species may be accomplished, for example, with acompressor and a valve system to increase the pressure in the vicinityof the cantilevered probe array. A condenser and a heater may be used,for example, to collect samples of the target chemical species and thenrelease it in proximity to the cantilevered probe array.

Selective attraction of chemical and biological species may beaccomplished with, for example, a species attraction potential appliedto a species attraction electrode disposed on at least one cantileveredprobe in the cantilevered probe array.

The self-sensed cantilevered probe array is exposed to a target chemicalspecies, as seen at block 110. The target chemical species may be in aliquid or a gas. A valve and associated piping may be used to expose thecantilevered probe array to the target chemical species and the carrier.

When embodied so, the resistive heater coupled to at least onecantilevered probe may be heated to react the target chemical species,as seen at block 112. Reaction of the target chemical species may beresult, for example, in a volatile material that is desorbed from one ormore cantilevered probes resulting in a shift in the resonant frequencydue to less mass on the beam. Alternatively, reaction of the targetchemical species may result in a formation of a material on the surfaceof the cantilevered probe that increases the vibrational stiffness ofthe cantilevered probe and produces a frequency shift. Alternatively,reaction of the target chemical species may result in a stressed film onthe surface of the cantilevered probe that causes a static deflection ofthe cantilevered probe, which may be measured, for example, with atapping mode where the cantilevered beam is tapped against a referencesurface adjusted to be a fixed distance away from the cantilevered beamor with a tapping mode where the beam is tapped against an adjustablemechanical stop, adjusted to allow the cantilevered probe to tap aconsistent amount against the mechanical stop.

The exposed cantilevered probe array is actuated, as seen at block 114.The exposed cantilevered probes are actuated, for example, by applyingan excitation voltage to a piezoelectric material disposed on eachcantilevered probe in the cantilevered probe array. In another example,the exposed cantilevered probe array is actuated with a frequencygenerator by scanning the cantilevered probes through a predeterminedfrequency range. In another example, the exposed cantilevered probearray is actuated by driving the exposed array at a resonant frequencyof one cantilevered probe in the cantilevered probe array, thenswitching as desired to a resonant frequency of another cantileveredprobe for additional measurements. In another example, the exposedcantilevered probe array is actuated by driving the exposed array at apredetermined frequency, wherein the predetermined frequency isoff-resonance with respect to at least one cantilevered probe in thecantilevered probe array. In another example, the amplitude of vibrationis controlled as the cantilevered probe strikes against a fixed oradjustable mechanical stop. In another example, the exposed cantileveredarray is actuated with an electrical impulse applied to the cantileveredprobe array.

A cantilevered probe response is detected from at least one self-sensedcantilevered probe in the cantilevered probe array, as seen at block116. Detecting the cantilevered probe response from one or more actuatedcantilevered probes comprises, for example, measuring a shifted resonantfrequency, a shifted Q factor, a shifted impedance, a shifted deflectionamplitude, and a combination thereof. A fast Fourier transform (FFT) maybe performed on the cantilevered probe response from one or moreactuated cantilevered probes. The entire array of cantilevered probes, asubset thereof, or an individual cantilevered probe may be addressed byselective actuation and detection.

With the availability of a reference cantilevered probe, a referencecantilevered probe response may be detected from one or more referencecantilevered probes in the cantilevered probe array.

The target chemical species is determined based on the detectedcantilevered probe response, as seen at block 118. A controller or asoftware application running on a computer or digital device may be usedto analyze the cantilevered probe responses and determine one or morecomponents and their concentration in the sample. The target chemicalspecies may be determined in part based on the detected referencecantilevered probe response, for example, by common mode correcting foreffects such as temperature, pressure and viscosity of the sampledmedium. The detected target chemical species may include, for example,mercury, hydrogen, an alcohol, water vapor, an explosive material, achemical element, a chemical compound, an organic material, an inorganicmaterial, a gaseous substance, a liquid, a biological material, a DNAstrand, a bioactive agent, a toxin, and combinations thereof.

Using pattern recognition, modeling functions or signal processingtechniques such as fuzzy logic, the target chemical species may bedetermined based on comparing a measured shift from one or more actuatedcantilevered probes to a reference set of cantilevered probe response,and determining the target chemical species based on the reference setof cantilevered probe responses. The reference set of cantilevered proberesponses may comprise, for example, a learned set from calibration runsor from a statistical database with expectation values for varioustarget chemical species.

FIG. 11 is a flow chart of a method for chemical detection, inaccordance with another embodiment of the present invention. Thechemical detection method includes various steps to detect and identifyone or more target chemical species with a self-sensed cantileveredprobe array.

A self-sensed cantilevered probe array is provided, as seen at block120. The cantilevered probes in the cantilevered probe array arefrequency-differentiated, and may include at least two series-connectedor parallel-connected cantilevered probes electrically connected to apair of cantilevered probe array drive pads. Alternatively, thecantilevered probe array includes a network of series-connected andparallel-connected cantilevered probes electrically connected to a pairof cantilevered probe array drive pads.

The array is initialized, as seen at block 122. Initialization of thearray is accomplished, for example, by running a scan through theresonant frequencies of the cantilevered probes in the cantileveredprobe array to establish a baseline or to ensure that all thecantilevered probes and the interface electronics are functioningproperly.

The self-sensed cantilevered probe array is exposed to a target chemicalspecies, as seen at block 124. The target chemical species may be in aliquid or a gas. A valve and associated piping may be used to expose thecantilevered probe array to the target chemical species and the carrier.

The exposed cantilevered probe array is actuated, as seen at block 126.The exposed cantilevered probes are actuated, for example, by applyingan excitation voltage to a piezoelectric material disposed on eachcantilevered probe in the cantilevered probe array; by scanning thecantilevered probes through a predetermined frequency range; by drivingthe exposed array at a resonant frequency of at least one cantileveredprobe in the cantilevered probe array; by driving the exposed array at apredetermined off-resonance frequency; by driving and controlling thetapping of the cantilevered probes against a fixed or adjustablemechanical stop; or by applying an electrical impulse to thecantilevered probe array.

A cantilevered probe response is detected from at least one self-sensedcantilevered probe in the cantilevered probe array and the targetchemical species is determined, as seen at block 128. Detecting thecantilevered probe response from one or more actuated cantileveredprobes comprises, for example, measuring a shifted resonant frequency, ashifted Q factor, a shifted impedance, a shifted deflection amplitude,and a combination thereof. A fast Fourier transform (FFT) may beperformed on the cantilevered probe response from one or more actuatedcantilevered probes to detect the target chemical species. The targetchemical species is determined based on the detected cantilevered proberesponse. The target chemical species may be determined based oncomparing a measured shift from one or more actuated cantilevered probesto a reference set of cantilevered probe responses, and determining thetarget chemical species based on the reference set of cantilevered proberesponses.

While the embodiments of the invention disclosed herein are presentlyconsidered to be preferred, various changes and modifications can bemade without departing from the spirit and scope of the invention. Thedetailed description and drawings are merely illustrative of theinvention rather than limiting, the scope of the invention being definedby the appended claims and equivalents thereof, and all variations andembodiments that come within the meaning and range of equivalents areembraced herein.

1-68. (canceled)
 69. A chemical detection system for detecting at least one target chemical species, comprising: a frequency-differentiated cantilevered probe array comprising a plurality of cantilevered probes, each cantilevered probe comprising: a piezoelectric layer; a treated section, wherein the treated sections of the plurality of cantilevered probes are different from one another; a first electrode electrically coupled to the piezoelectric layer; and a second electrode electrically coupled to the piezoelectric layer; a first electrical lead electrically coupled to a first electrode of at least one of the plurality of cantilevered probes and in electrical communication with the first electrode of each of the plurality of cantilevered probes; a second electrical lead electrically coupled to a second electrode of at least one of the plurality of cantilevered probes and in electrical communication with the second electrode of each of the plurality of cantilevered probes; an interface circuit electrically coupled to the first and second electrical leads and configured to actuate the cantilevered probes; a sensing circuit electrically coupled to the first and second electrical leads; and wherein the cantilevered probes are actuated when, through the first and second leads, a drive voltage is applied to the piezoelectric layer by the interface circuit thus generating an electrical response transmitted to the sensing circuit and at least one cantilevered probe in the array exhibits a shifted electrical response when the cantilevered probe array is exposed to the target chemical species and the at least one cantilevered probe is actuated by the interface circuit as a result of the exposure of the treated section to the target chemical species.
 70. The chemical detection system of claim 69 wherein the first and second electrodes of the plurality of cantilevered probes are electrically coupled to one another, the plurality of cantilevered probes thus being connected in series to the first and second leads.
 71. The chemical detection system of claim 69 wherein the first lead is electrically coupled to the first electrode of each of the plurality of cantilevered probes and the second lead is electrically coupled to the second electrode of each of the plurality of cantilevered probes, the first and second leads thus being connected in parallel to the plurality of cantilevered probes.
 72. The chemical detection system of claim 69 wherein the cantilevered probe array comprises a network of series-connected and parallel-connected cantilevered probes electrically connected to a pair of cantilevered probe array drive pads.
 73. The chemical detection system of claim 69 wherein the interface circuit comprises an adjustable frequency generator that is scanned through a predetermined frequency range.
 74. The chemical detection system of claim 69 wherein the interface circuit comprises an impedance analyzer that is scanned through a resonant frequency of the at least one cantilevered probe in the cantilevered probe array.
 75. The chemical detection system of claim 69 wherein the interface circuit comprises an oscillator circuit operating at a resonant frequency of the at least one cantilevered probe in the cantilevered probe array.
 76. The chemical detection system of claim 69 wherein the interface circuit comprises an oscillator circuit operating at a predetermined frequency, wherein the predetermined frequency is off-resonance with respect to the at least one cantilevered probe in the cantilevered probe array.
 77. The chemical detection system of claim 69 wherein the interface circuit comprises an impulse circuit for applying an electrical impulse to the cantilevered probe array.
 78. The chemical detection system of claim 69 wherein the interface circuit includes a fast Fourier transform generator to perform a fast Fourier transform on the shifted cantilevered probe response.
 79. The chemical detection system of claim 69 wherein the interface circuit detects a shifted electrical response from the at least one actuated cantilevered probe.
 80. The chemical detection system of claim 79 wherein the shifted electrical response comprises one of a shifted resonant frequency, a shifted Q factor, a shifted impedance, and a shifted deflection amplitude.
 81. The chemical detection system of claim 69 further comprising: a controller in communication with the interface circuit; wherein the controller receives a shifted electrical response from a set of cantilevered probes in the cantilevered probe array, and wherein the target chemical species is determined based on the shifted electrical response.
 82. The chemical detection system of claim 69 further comprising: a controller in communication with the interface circuit; wherein the controller receives a shifted electrical response from a set of cantilevered probes in the cantilevered probe array, and wherein the target chemical species is determined based on a comparison between the shifted electrical response and a reference set of electrical responses.
 83. The chemical detection system of claim 82 wherein the reference set of electrical responses comprises measured responses from known exposure conditions.
 84. The chemical detection system of claim 69 wherein the chemical-sensitive coating material comprises a coating applied through a mask disposed on a portion of the at least one cantilevered probe.
 85. The chemical detection system of claim 69 wherein the chemical-sensitive coating material comprises a non-homogeneous coating material applied to a set of cantilevered probes in the cantilevered probe array.
 86. The chemical detection system of claim 69 further comprising: a reference cantilevered probe in the cantilevered probe array, wherein the reference cantilevered probe provides a reference electrical response when the cantilevered probe array is exposed to the target chemical species.
 87. The chemical detection system of claim 69 further comprising: a species attraction electrode disposed on the at least one cantilevered probe in the cantilevered probe array to allow application of a species attraction potential.
 88. The chemical detection system of claim 69, wherein a resistive heater is coupled to at least one cantilevered probe in the cantilevered probe array and the chemical detection system further comprises a heater circuit electrically coupled to the resistive heater. 